WO2023082219A1 - 一种高效制备金属有机框架负载硒原子的纳米复合材料方法和应用 - Google Patents

一种高效制备金属有机框架负载硒原子的纳米复合材料方法和应用 Download PDF

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WO2023082219A1
WO2023082219A1 PCT/CN2021/130492 CN2021130492W WO2023082219A1 WO 2023082219 A1 WO2023082219 A1 WO 2023082219A1 CN 2021130492 W CN2021130492 W CN 2021130492W WO 2023082219 A1 WO2023082219 A1 WO 2023082219A1
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selenium
powder
zif
beaker
organic framework
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French (fr)
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贺利贞
陈填烽
陈义康
袁中文
李海伟
许宇龙
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广东暨创硒源纳米研究院有限公司
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Priority to PCT/CN2021/130492 priority Critical patent/WO2023082219A1/zh
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/04—Sulfur, selenium or tellurium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
    • A61K47/69—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the conjugate being characterised by physical or galenical forms, e.g. emulsion, particle, inclusion complex, stent or kit
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery

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  • This patent relates to the technical field of chemical material preparation, in particular to a metal organic framework loaded selenium atom nanocomposite material and its preparation method and application.
  • MOFs Metal-organic frameworks
  • ZIF-67 is the framework material of imidazole molecular sieve, which is a porous metal organic framework material, and Zif-8 is a zeolite imidazole framework material, which is a new type of porous material, which combines the high stability of inorganic molecular sieves and the high performance of MOFS. Porosity and organic functionality.
  • the combination preparation method of MOF and selenium is mainly through physical stirring to achieve in-situ encapsulation.
  • the yield of this method is usually low and uncontrollable, and it is difficult to achieve large-scale or large-scale production.
  • the method of synthesizing MOF is used to realize the encapsulation of selenium nanomaterials, and the selenium nanomaterials are evenly mixed with the metal salt solution forming MOF, and then the ligand is added to start the reaction of MOF formation.
  • This method is affected by the size of selenium nanomaterials, and only small sizes can be used for synthesis.
  • the selenium content of materials prepared by different MOFs will also vary.
  • the existing preparation technology also adopts the tube furnace vapor deposition method, which is to obtain selenium vapor by heating selenium powder at one end of the tube, and drive the selenium gas to the other section of the tube under the flow of nitrogen or argon to carry the selenium gas.
  • the primary purpose of the present invention is to provide a method for efficiently preparing a nanocomposite material with selenium atoms supported by a metal organic framework.
  • Another object of the present invention is to provide a nanocomposite material in which selenium atoms are loaded on a metal organic framework.
  • Another object of the present invention is to provide the nano-composite material of the metal-organic framework loaded with selenium atoms in anti-oxidation therapy and biopharmaceutical applications.
  • a method for efficiently preparing a nanocomposite material with a metal-organic framework loaded with selenium atoms comprising the steps of:
  • the heating container is a quartz glass tube, and the evacuated quartz glass tube is sealed at high temperature by a hydrogen flame, and the sealed quartz glass tube is placed in a high-temperature furnace, heated to 230-280°C, and kept at a constant temperature of 0.5-1.5°C. Hour.
  • the preparation method of the nanocomposite material with selenium atoms supported by the metal organic framework also includes the step of preparing ZIF-67 powder or ZIF-8 powder,
  • ZIF-8 powder pour zinc nitrate hexahydrate into beaker A, add methanol and mix; in addition, pour 2-methylimidazole into beaker B, add methanol and mix; Then, pour the solution in beaker A and beaker B into a large beaker and mix them together, seal the mouth of the beaker and react under vigorous stirring for 1-2 hours, centrifuge and spin, collect the product and wash it with methanol, and dry it to get ZIF- 8 powder.
  • the selenium doping content of the nanocomposite material of the metal-organic framework loaded with selenium atoms can be adjusted Up to 35-48%.
  • the invention also provides a nanocomposite material in which metal organic framework supports selenium atoms, which is obtained by adopting the above preparation method. Specifically, a Se/ZIF-67 composite system material or a Se/ZIF-8 composite system material is obtained. The nano-composite material containing selenium has anti-oxidation effect.
  • the present invention also provides the application of the above-mentioned preparation method in biopharmaceuticals to obtain a nanocomposite material with selenium atoms supported by the metal organic framework.
  • the metal-organic framework-loaded nanocomposite material with selenium atoms has a protective effect on human neuroblastoma cells, and can be made into an oral agent drug or intravenous injection drug with the effect of treating stroke; the metal-organic framework-loaded nanometer composite material with selenium atoms Composite materials can also be used in biocatalytic therapeutic applications.
  • the nano-composite material of metal-organic framework loaded selenium atom that the preparation method of the present invention obtains is the MOF nanomaterial with catalytic ability
  • nano-selenium has the functions of anti-oxidation, free radical scavenging and anti-inflammation, and the advantages of metal-organic framework materials such as large specific surface area and high porosity.
  • the composite material has a large loading capacity. Through elemental analysis under a high-resolution transmission electron microscope, it is found that selenium is evenly distributed in the MOF, and the surface is successfully doped with selenium.
  • the MOF basically maintains the original morphology framework, which is better than the existing preparation methods of MOF and MOF.
  • the binding material of selenium is more excellent.
  • the preparation method of the present invention especially adopts the form of vacuum sealing tube so that selenium will not be discharged when heated at high temperature. Sealed and heated to 230-280°C, and kept at a constant temperature for a period of time, the fusion reaction effect of ZIF-8 powder or ZIF-67 powder and nano-selenium powder is the best, and the selenium and MOF are realized in a closed space as the temperature decreases. More than 95% of the materials are closely combined without leakage, and the selenium doping content of the composite material reaches 35-48%.
  • the preparation method of the present invention can conveniently control the mixing ratio of the MOF material and selenium powder, adjust the content of loaded selenium according to the needs of pharmaceuticals, and overcome the shortcoming of the small synthesis scale of the physical stirring method, which can effectively reduce the waste of raw materials and realize efficient conversion and utilization. Realize the best use of everything and provide an innovative solution for the large-scale synthesis of selenium MOF nanomaterials. It can also overcome the loss of most of the selenium with the gas caused by the existing preparation method (tube furnace vapor deposition method), the low selenium doping amount is only 5-16%, the doping amount is uncontrollable and the selenium gas is easy to cause the tube furnace Pollution of the pipe, the disadvantages of high maintenance costs.
  • the present invention selects two typical MOF materials, and uses these two typical MOF materials as the carrier of nano-selenium, and uses the method of vacuum sealing to innovatively prepare the composite nano-material of selenium MOF, and loads nano-selenium for other MOF materials.
  • Selenium provides a reference, a reference for loading other elements on MOF, and a technical reference for loading dual or multi-element substances on MOF.
  • the present invention also provides the application of the above-mentioned preparation method to obtain a nanocomposite material of a metal organic framework loaded with selenium atoms in biopharmaceuticals, and the nanocomposite material of the metal organic framework loaded with selenium atoms can be made into a drug for treating brain diseases Agent drug taken orally or given intravenously; used especially in the treatment of stroke.
  • the nano-composite material with selenium atoms supported by the metal-organic framework can also be used in biocatalysis applications, which greatly expands the application field of the selenium-containing nano-composite material based on the metal-organic framework, and has broad application prospects in medicine and medicine.
  • the raw materials of composite materials are cheap and easy to obtain, the synthesis and operation steps are highly operable, and there is no pollution to the environment.
  • the synthesis scale can be immediately expanded to realize the commercialization and application of drugs.
  • Fig. 1 is the transmission electron micrograph and powder photo of ZIF-67 powder and Se/ZIF-67 composite system material doped with different selenium content of the present invention.
  • Fig. 2 is the transmission electron micrograph and powder photo of ZIF-8 powder and Se/ZIF-8 composite system material doped with different selenium content of the present invention.
  • Fig. 5 It is the nanocomposite material of the metal-organic framework of the present invention loaded with selenium atoms, corresponding to the XRD patterns of different mass ratios (Se:ZIF-67).
  • Fig. 6 It is the nanocomposite material of the metal organic framework supporting selenium atoms of the present invention, corresponding to the XRD patterns of different mass ratios (Se:ZIF-8).
  • Figure 7 It is a comparison chart of detection using ABTS total antioxidant capacity detection method.
  • Figure 8 Comparison of the protective effects of the metal-organic framework-supported nanocomposite material of the present invention on human brain neuroblastoma cells (SH-SY5Y).
  • the invention provides a method for preparing a nanocomposite material in which a metal organic framework supports selenium atoms, comprising the steps of:
  • nano-selenium powder is purchased from Aladdin (article number: S105193; Purity: 99.9%), the heating container is evacuated into a vacuum state, such as utilizing the vacuum sealing system of Guangzhou Shanzhun Instrument Co., Ltd.
  • the heating container is a quartz glass tube, and the evacuated quartz glass tube is sealed at high temperature by a hydrogen flame.
  • the sealed quartz glass tube is placed in a high-temperature furnace, heated to 230-280° C., and kept at a constant temperature for 0.5-1.5 hours.
  • the quartz glass tube can be evacuated to a vacuum using a vacuum sealing system, and the quartz glass tube can be heated with a hydrogen flame for 3-5 minutes, and the inner glass plug is bonded to the glass wall until the seal is intact.
  • ZIF-67 powder or ZIF-8 powder can be used, or ZIF-67 powder or ZIF-8 powder can be prepared according to the following steps.
  • ZIF-8 powder pour zinc nitrate hexahydrate into beaker A, add methanol and mix; in addition, pour 2-methylimidazole into beaker B, add methanol and mix; Then, pour the solution in beaker A and beaker B into a large beaker and mix them together, seal the mouth of the beaker and react under vigorous stirring for 1-2 hours, centrifuge and spin, collect the product and wash it with methanol, and dry it to get ZIF- 8 powder.
  • Embodiment 1 a method for preparing a nanocomposite material with selenium atoms supported by a metal organic framework, comprising the steps of:
  • Embodiment 2 a method for preparing a nanocomposite material with selenium atoms supported by a metal organic framework, comprising the steps of:
  • the nanocomposite material of the metal-organic framework loaded with selenium atoms obtained by the above preparation method was tested by experiment.
  • Fig. 1 is a transmission electron microscope image and a powder photo of ZIF-67 powder and Se/ZIF-67 composite system material doped with different selenium contents of the present invention.
  • the lower right corner of the powder photo is a histogram of the mass percentage of selenium, which is detected by an atomic fluorescence spectrometer.
  • the selenium content of the composite material of the present invention is higher than that of the existing metal-organic frameworks.
  • Fig. 2 is a transmission electron micrograph and a powder photo of ZIF-8 powder and Se/ZIF-8 composite system material doped with different selenium contents of the present invention.
  • the selenium content of the composite material of the present invention is higher than that of the existing metal-organic frameworks.
  • Fig. 5 is a nanocomposite material with selenium atoms supported by the metal organic framework of the present invention, corresponding to XRD patterns of different mass ratios (Se:ZIF-67).
  • Fig. 6 is a nanocomposite material with selenium atoms supported by a metal organic framework of the present invention, corresponding to XRD patterns of different mass ratios (Se:ZIF-8).
  • the characteristic crystal plane information of the composite material of the present invention can be analyzed, that is, different materials have different crystal plane information.
  • the crystal plane information corresponding to MOF materials with or without selenium doping it was found that the basic crystal plane information of MOF after selenium doping was preserved, and no new crystal plane information was displayed, indicating that the composite material was successfully doped with selenium.
  • Figure 7 is the use of the ABTS total antioxidant capacity detection method to detect the antioxidant capacity of different mass ratios (Se:ZIF-67) based on metal-organic framework selenium-containing nanocomposites. It can be seen that the selenium-containing nanocomposites based on metal-organic frameworks have Significant antioxidant capacity, 100ug/mL can achieve close to 95% removal effect.
  • sodium selenite, sodium selenate, selenocysteine, selenomethionine, chitosan-modified nano-selenium, lentinan-modified nano-selenium, and metal-organic framework-based selenium-containing The antioxidant capacity of the nanocomposites was tested. Among them, sodium selenite, sodium selenate, selenocysteine, selenomethionine, chitosan-modified nano-selenium, and lentinan-modified nano-selenium all showed an antioxidant effect lower than 5-10%.
  • Figure 8 is the selection of the human brain neuroblastoma cell line (SH-SY5Y) as the object of the cell model, by adding 20 ⁇ M tert-butyl hydroperoxide to simulate the free radicals produced by the cells, and finally detecting the SH-SY5Y by flow cytometry
  • the apoptosis ratio of SY5Y cells was used to evaluate the protective effect of metal organic framework nanocomposites loaded with selenium atoms on SH-SY5Y cells in the free radical damage model versus cell damage model.
  • the present invention also provides the application of the above-mentioned preparation method in biopharmaceuticals to obtain a nanocomposite material with a metal-organic framework loaded with selenium atoms.
  • the nano-composite material of the metal-organic framework loaded with selenium atoms can be made into an oral reagent drug or an intravenous drug for the treatment of stroke, which greatly expands the application field of the selenium-containing nano-composite material based on the metal-organic framework, and has broad medical applications. Pharmaceutical application prospects.
  • the nano-composite material of metal-organic framework loaded selenium atom that the preparation method of the present invention obtains is the MOF nanomaterial with catalytic ability Combined with selenium, nano-selenium has the functions of anti-oxidation, free radical scavenging and anti-inflammation, and the advantages of metal-organic framework materials such as large specific surface area and high porosity.
  • the composite material has a large specific surface area and a large loading capacity.
  • the preparation method of the present invention especially adopts the form of vacuum sealing tube so that selenium will not be discharged when heated at high temperature. Sealed and heated to 230-280°C, and kept at a constant temperature for a period of time, the fusion reaction effect of ZIF-8 powder or ZIF-67 powder and nano-selenium powder is the best, and the selenium and MOF are realized in a closed space as the temperature decreases. More than 95% of the materials are closely combined without leakage, and the selenium doping content of the composite material reaches 35-48%.
  • the inventors have found that high-temperature vacuum sealing heating to 230-280°C can prevent the material from reacting with oxygen in the air, improve the material purity and catalytic rate, and if the temperature is lower than 230°C, MOF and selenium cannot be well combined; if the temperature is higher than 280°C °C, the porosity of the composite material becomes smaller and the catalytic rate is lower.
  • the metal-organic framework-loaded nanocomposite material with selenium atoms prepared by the inventor has a high utilization rate of selenium atoms, reaching 80-95%. Compared with the selenium MOF material fired in a tube furnace, the selenium utilization rate is increased by 20% -70%, can effectively reduce the waste of raw materials to achieve efficient conversion and utilization, and provide an innovative solution for large-scale synthesis of selenium MOF nanomaterials.
  • the metal organic framework loaded with selenium atoms has better water solubility, water dispersibility, and better antioxidant effect. Under the condition of selenium content, the antioxidant activity increases by 30-70%.
  • the metal-organic framework-supported nanocomposite material prepared by the inventors has a better protective effect on human neuroblastoma cells than the single nano-selenium, MOF or the selenium-MOF composite material prepared above 700 °C, It has a good therapeutic effect in the treatment of stroke.

Abstract

一种高效制备金属有机框架负载硒原子的纳米复合材料方法和应用，其制备方法包括步骤：(1)称取ZIF-67粉末和硒粉，其质量比ZIF-67粉末:硒粉＝1-50:1，或者称取ZIF-8粉末和硒粉，其质量比ZIF-8粉末:硒粉＝1-50:1，混合均匀后倒入加热容器中，将加热容器抽成真空状态，高温密封加热至230-280℃，并保持恒温一段时间，自动冷却后取出加热容器，倒出混合物得到金属有机框架负载硒原子的纳米复合材料。金属有机框架负载硒原子的纳米复合材料具有更佳的人神经母细胞瘤细胞保护效果，在脑卒中的治疗中具有良好效果。

Description

一种高效制备金属有机框架负载硒原子的纳米复合材料方法和应用 技术领域
本专利涉及化学材料制备技术领域，特别涉及金属有机框架负载硒原子纳米复合材料及制备方法和应用。
背景技术
金属有机框架(MOF)具有分子/原子水平的催化中心、高孔隙率、大表面积、高负载能力和均匀结构，作为一类二维或三维多孔晶体材料，在过去的10年中，已成为快速和重要的催化剂设计最有希望的材料之一。在生物医药分子存储、多相催化、生物医药输送、气体分离和能量存储应用方面显示出巨大的潜力。硒作为人体必需微量元素之一，对健康维护和疾病预防有很大的支持作用。MOF与硒的结合将有希望在生物医药领域开发更多的可能性。
ZIF-67是咪唑分子筛的骨架材料，它是一种多孔金属有机骨架材料，Zif-8是沸石咪唑骨架材料，它是一种新型多孔材料，它结合了无机分子筛的高稳定性和MOFS的高孔隙率和有机功能。
目前，MOF与硒的结合制备方式是主要通过物理搅拌实现原位包裹的方法，这种方法产量通常较低且不可控，难于实现大批量或者规模化生产。具体是，用合成MOF的方法实现对硒纳米材料的包裹，硒纳米材料与形成MOF的金属盐溶液混合均匀后再加入配体启动MOF形成的反应。该方法受到硒纳米材料大小的影响，小尺寸才能用于合成，同时不同的MOF制备出来的材料硒含量也会各有不同。
另外，现有制备技术还采用管式炉气相沉积法，是通过在管子一端加热硒粉得到硒蒸汽，在氮气或氩气的流动下带动硒气体往管子的另一段携带，硒气体遇到后端较低温区时沉积至材料上形成硒掺杂的方法。该方法中往往大量的 硒气体随氮气或氩气流排出，大部分硒随气体损耗，因此硒掺杂量低只达5-16％，大部分硒随气体损耗，掺杂量不可控并且硒气体容易造成管式炉管的污染，维护成本较高，且跟温度区间设置有重要关系，不容易控制大规模生产。
因此有必要对MOF基的含硒材料制备工艺进行改进，得到性能更好的基于金属有机框架的含硒材料。
发明内容
针对现有技术的不足，本发明的首要目的是提供一种高效制备金属有机框架负载硒原子的纳米复合材料的方法。
本发明的另一目的是提供一种金属有机框架负载硒原子的纳米复合材料。
本发明的另一目的是提供金属有机框架负载硒原子的纳米复合材料在抗氧化治疗，生物制药方面的应用。
本发明的目的通过下述技术方案实现：
一种高效制备金属有机框架负载硒原子的纳米复合材料方法，包括步骤：
称取ZIF-67粉末和硒粉，其质量比ZIF-67粉末:硒粉＝1-50:1，混合均匀后倒入加热容器中，将所述加热容器抽成真空状态，高温密封加热至230-280℃，并保持恒温一段时间，自动冷却后取出所述加热容器，倒出混合物得到金属有机框架负载硒原子的纳米复合材料(即Se/ZIF-67复合体系材料)；
或者，称取ZIF-8粉末和硒粉，其质量比ZIF-8粉末:硒粉＝1-50:1，混合均匀后倒入加热容器中，将所述加热容器抽成真空状态，高温密封加热至230-280℃，并保持恒温一段时间，自动冷却后取出所述加热容器，倒出混合物得到金属有机框架负载硒原子的纳米复合材料(即Se/ZIF-8复合体系材料)。
进一步，所述加热容器是石英玻璃管，抽成真空的石英玻璃管通过氢火焰高温密封，将密封好的石英玻璃管置于高温炉内，升温至230-280℃，并保持恒温0.5-1.5小时。
具体的，利用真空封管***将石英玻璃管抽至真空，利用氢火焰加热石英 玻璃管3-5分钟，内玻璃塞与玻璃壁贴合，直至密封完好。
进一步，所述金属有机框架负载硒原子的纳米复合材料制备方法，还包括制备ZIF-67粉末，或者ZIF-8粉末的步骤，
其中制备ZIF-67粉末，取六水合硝酸钴倒入烧杯A中，加入甲醇混合；另外将2-甲基咪唑倒入烧杯B中，加入甲醇混合；上述烧杯A和烧杯B中溶液分别在超声波处理下充分溶解；再将烧杯A和烧杯B中溶液倒入大烧杯混合在一起，密封烧杯口后在剧烈搅拌下反应6-10小时，离心旋转处理，收集产物并用甲醇清洗，干燥后得到ZIF-67粉末；
制备ZIF-8粉末，取六水合硝酸锌倒入烧杯A中，加入甲醇混合；另外将2-甲基咪唑倒入烧杯B中，加入甲醇混合；上述烧杯A和烧杯B中溶液分别在超声波处理下充分溶解；再将烧杯A和烧杯B中溶液倒入大烧杯混合在一起，密封烧杯口后在剧烈搅拌下反应1-2小时，离心旋转处理，收集产物并用甲醇清洗，干燥后得到ZIF-8粉末。
进一步，根据控制所述ZIF-67粉末和纳米硒粉混合比例，或者根据控制ZIF-8粉末和纳米硒粉混合比例，可调节所述金属有机框架负载硒原子的纳米复合材料的硒掺杂含量达35-48％。
本发明还提供一种金属有机框架负载硒原子的纳米复合材料，是采用上述制备方法得到。具体是得到Se/ZIF-67复合体系材料，或者是Se/ZIF-8复合体系材料。所述含硒纳米复合材料具有抗氧化作用。
本发明还提供上述制备方法得到一种金属有机框架负载硒原子的纳米复合材料在生物制药方面的应用。
所述金属有机框架负载硒原子的纳米复合材料，具有人神经母细胞瘤细胞保护作用，可制成有治疗脑卒中作用的口服试剂药物或静脉注射药物；所述金属有机框架负载硒原子的纳米复合材料还可用于生物催化治疗应用中。
本发明方案相对于现有技术具有如下的优点及效果：
(1)本发明制备方法得到的金属有机框架负载硒原子的纳米复合材料，比 如Se/ZIF-67复合体系材料，或者是Se/ZIF-8复合体系材料，是把具有催化能力的MOF纳米材料与硒相结合，充分发挥纳米硒具有抗氧化，清除自由基和抗炎的功能，以及金属有机框架材料大比表面积、高孔隙率等优点。复合材料负载量大，通过高分辨透射电子显微镜下的元素分析，发现硒在MOF中均匀分布，表面硒的成功掺杂，而且MOF基本保持原本的形貌框架，比现有制备方式的MOF与硒的结合材料更优异。
(2)对比现有的两种基于MOF含硒的制备方法，本发明制备方法特别采用抽真空封管的形式让硒在高温加热时不会排出，还通过几百次试验发现，在高温真空密封加热至230-280℃，并保持恒温一段时间，ZIF-8粉末或ZIF-67粉末分别与纳米硒粉的融合反应效果最佳，而且是在密闭空间内随着温度的降低实现硒与MOF材料95％以上的紧密结合，没有泄露，复合材料的硒掺杂含量达35-48％。
发明人试验发现高温真空密封加热至230-280℃可防止材料和空气中氧气反应，提高材料纯度和催化率，其加热温度范围值的选择是通过大量创新实验得到的最佳值，如果温度低于230℃，MOF和硒不能很好结合；如果温度高于280℃，复合材料的孔隙率变小，催化率低。
另外，本发明制备方法可方便控制所述MOF材料和硒粉混合比例，按照制药的需求调节负载硒的含量，并克服物理搅拌法合成规模小的缺点，可有效减少原料浪费实现高效转化利用，实现物尽其用，为大规模合成硒MOF纳米材料提供一种创新的方案。还可克服现有制备方法(管式炉气相沉积法)带来大部分硒随气体损耗，硒掺杂量低只达5-16％，掺杂量不可控并且硒气体容易造成管式炉炉管的污染，维护成本较高的缺点。
(3)本发明通过选取两种典型MOF材料，并用这两种典型的MOF材料作为纳米硒的载体，利用真空封管的方法创新的制备出硒MOF的复合纳米材料，为其他MOF材料负载纳米硒提供了参考,为MOF负载其他元素提供的参考，也为MOF负载双或多元素物质提供了技术参考。
(4)本发明还提供上述制备方法得到一种金属有机框架负载硒原子的纳米复合材料在生物制药方面的应用，所述金属有机框架负载硒原子的纳米复合材料可制成有治疗大脑疾病的口服试剂药物或静脉注射药物；特别用于治疗脑卒中。所述金属有机框架负载硒原子的纳米复合材料还可用于生物催化应用中，大大扩展了基于金属有机框架的含硒纳米复合材料的应用领域，具有广阔的医学药物应用前景。
复合材料原料廉价易得，合成和操作步骤可操作性强，没有污染环境，可马上扩大合成规模，实现药物的商业化和应用。
附图说明
图1：是ZIF-67粉末与本发明不同硒含量掺杂的Se/ZIF-67复合体系材料的透射电镜图与粉末照片。
图2：是ZIF-8粉末与本发明不同硒含量掺杂的Se/ZIF-8复合体系材料的透射电镜图与粉末照片。
图3：是本发明金属有机框架负载硒原子的纳米复合材料，对应Se:ZIF-67＝1:5时的元素分析图谱。
图4：是本发明金属有机框架负载硒原子的纳米复合材料，对应Se:ZIF-8＝1:5时的元素分析图谱。
图5：是本发明金属有机框架负载硒原子的纳米复合材料，对应不同质量比(Se:ZIF-67)的XRD图谱。
图6：是本发明金属有机框架负载硒原子的纳米复合材料，对应不同质量比(Se:ZIF-8)的XRD图谱。
图7：是使用ABTS总抗氧化能力检测法进行检测对比图。
图8：是本发明金属有机框架负载硒原子的纳米复合材料，对人脑神经母细胞瘤细胞(SH-SY5Y)的保护效果对比。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
本发明提供一种金属有机框架负载硒原子的纳米复合材料制备方法，包括步骤：
称取ZIF-67粉末和硒粉，其质量比ZIF-67粉末:硒粉＝1-50:1，混合均匀后倒入加热容器中，纳米硒粉购买自阿拉丁(货号：S105193；纯度：99.9％)，将所述加热容器抽成真空状态，比如利用广州善准仪器有限公司的真空封管***将石英玻璃管抽至真空(-15Pa)，高温密封加热至230-280℃，并保持恒温0.5-1.5小时，自动冷却后取出所述加热容器，倒出混合物得到基于金属有机框架的含硒纳米复合材料(即Se/ZIF-67复合体系材料)；
或者，称取ZIF-8粉末和纳米硒粉，其质量比ZIF-8粉末:硒粉＝1-50:1，混合均匀后倒入加热容器中，将所述加热容器抽成真空状态，高温密封加热至230-280℃，并保持恒温0.5-1.5小时，自动冷却后取出所述加热容器，倒出混合物得到金属有机框架负载硒原子的纳米复合材料(即Se/ZIF-8复合体系材料)。
所述加热容器是石英玻璃管，抽成真空的石英玻璃管通过氢火焰高温密封，将密封好的石英玻璃管置于高温炉内，升温至230-280℃，并保持恒温0.5-1.5小时。具体可利用真空封管***将石英玻璃管抽至真空，利用氢火焰加热石英玻璃管3-5分钟，内玻璃塞与玻璃壁贴合，直至密封完好。
当然可以采用现有购买的ZIF-67粉末，或ZIF-8粉末，也可以按照下述步骤制备ZIF-67粉末，或者ZIF-8粉末。
制备ZIF-67粉末，取六水合硝酸钴倒入烧杯A中，加入甲醇混合；另外将2-甲基咪唑倒入烧杯B中，加入甲醇混合；上述烧杯A和烧杯B中溶液分别在超声波处理下充分溶解；再将烧杯A和烧杯B中溶液倒入大烧杯混合在一起，密封烧杯口后在剧烈搅拌下反应6-10小时，离心旋转处理，收集产物并用甲醇清洗，干燥后得到ZIF-67粉末；
制备ZIF-8粉末，取六水合硝酸锌倒入烧杯A中，加入甲醇混合；另外将2-甲基咪唑倒入烧杯B中，加入甲醇混合；上述烧杯A和烧杯B中溶液分别在超声波处理下充分溶解；再将烧杯A和烧杯B中溶液倒入大烧杯混合在一起，密封烧杯口后在剧烈搅拌下反应1-2小时，离心旋转处理，收集产物并用甲醇清洗，干燥后得到ZIF-8粉末。
实施例一，金属有机框架负载硒原子的纳米复合材料制备方法，包括步骤：
(一)ZIF-67的制备
称取0.733g六水合硝酸钴于100mL烧杯A，加入50mL甲醇，将1.623g 2-甲基咪唑于另外的100mL烧杯B中，加入50mL甲醇。上述烧杯A和烧杯B中溶液分别在超声波处理下充分溶解。再将烧杯A和烧杯B中溶液倒入大烧杯混合在一起，密封烧杯口后在剧烈搅拌下反应8h。最后在12000rpm转速下离心收集产物并用甲醇洗三次，置于60℃干燥箱烘干得到ZIF-67粉末。
(二)Se/ZIF-67的制备
称取50mg ZIF-67粉末和不同质量比的硒粉(比如ZIF-67:硒粉＝10:1)，混合均匀后倒入石英玻璃管中，利用真空封管***将石英玻璃管抽至真空(-15Pa)，再利用氢氧机制备氢火焰在真空状态下，氢火焰高温密封石英玻璃管，内玻璃塞与玻璃壁贴合，直至密封完好。最后将密封好的石英管置于马弗炉内，5℃/min升温至230℃，并保持恒温1h。自动冷却后取出石英玻璃管，得到Se/ZIF-67复合体系材料。
(三)ZIF-8的制备
称取1.2g六水合硝酸锌于100mL烧杯A，加入41mL甲醇；称取2.65g 2-甲基咪唑于另外的100mL烧杯B中，加入41mL甲醇。上述烧杯A和烧杯B中溶液分别在超声波处理下充分溶解。再将烧杯A和烧杯B中溶液倒入大烧杯混合在一起，密封烧杯口后在剧烈搅拌下反应1h。最后在12000rpm转速下离心收集产物并用甲醇洗三次，置于60℃干燥箱烘干得到ZIF-8粉末。
(四)Se/ZIF-8的制备
称取50mg ZIF-8粉末和不同质量比的硒粉(如ZIF-8:硒粉＝10:1)，混合均匀后倒入石英玻璃管中，利用真空封管***将石英玻璃管抽至真空(-15Pa)，再利用氢氧机制备氢火焰在真空状态下，氢火焰高温密封石英玻璃管，内玻璃塞与玻璃壁贴合，直至密封完好。最后将密封好的石英管置于马弗炉内，5℃/min升温至230℃，并保持恒温1h。自动冷却后取出石英玻璃管，得到Se/ZIF-8复合体系材料。
实施例二，金属有机框架负载硒原子的纳米复合材料制备方法，包括步骤：
(一)ZIF-67的制备
称取0.9g六水合硝酸钴于100mL烧杯A，加入50mL甲醇，将1.8g 2-甲基咪唑于另外的100mL烧杯B中，加入50mL甲醇。上述烧杯A和烧杯B中溶液分别在超声波处理下充分溶解。再将烧杯A和烧杯B中溶液倒入大烧杯混合在一起，密封烧杯口后在剧烈搅拌下反应10h。最后在12000rpm转速下离心收集产物并用甲醇洗三次，置于60℃干燥箱烘干得到ZIF-67粉末。
(二)Se/ZIF-67的制备
称取50mg ZIF-67粉末和不同质量比的硒粉(比如ZIF-67:硒粉＝1:1)，混合均匀后倒入直径14mm，长280mm的石英玻璃管中，利用真空封管***将石英玻璃管抽至真空(-15Pa)，再利用氢氧机制备氢火焰在真空状态下，氢火焰高温密封石英玻璃管，内玻璃塞与玻璃壁贴合，直至密封完好。最后将密封好的石英管置于马弗炉内，5℃/min升温至260℃，并保持恒温1.5h。自动冷却后取出石英玻璃管，得到Se/ZIF-67复合体系材料。
(三)ZIF-8的制备
称取1.5g六水合硝酸锌于100mL烧杯A，加入43mL甲醇；称取2.8g 2-甲基咪唑于另外的100mL烧杯B中，加入43mL甲醇。上述烧杯A和烧杯B中溶液分别在超声波处理下充分溶解。再将烧杯A和烧杯B中溶液倒入大烧杯混合在一起，密封烧杯口后在剧烈搅拌下反应2h。最后在12000rpm转速下离心收集产物并用甲醇洗三次，置于60℃干燥箱烘干得到ZIF-8粉末。
(四)Se/ZIF-8的制备
称取50mg ZIF-8粉末和不同质量比的硒粉(如ZIF-8:硒粉＝1:1)，混合均匀后倒入直径14mm，长280mm的石英玻璃管中，利用真空封管***将石英玻璃管抽至真空(-15Pa)，再利用氢氧机制备氢火焰在真空状态下，氢火焰高温密封石英玻璃管，内玻璃塞与玻璃壁贴合，直至密封完好。最后将密封好的石英管置于马弗炉内，5℃/min升温至260℃，并保持恒温1.5h。自动冷却后取出石英玻璃管，得到Se/ZIF-8复合体系材料。
通过试验检测上述制备方法得到的金属有机框架负载硒原子的纳米复合材料。
图1是ZIF-67粉末与本发明不同硒含量掺杂的Se/ZIF-67复合体系材料的透射电镜图与粉末照片。分别取质量比ZIF-67:硒粉＝1:1，ZIF-67:硒粉＝5:1，ZIF-67:硒粉＝10:1，ZIF-67:硒粉＝20:1，ZIF-67:硒粉＝40:1。可见当粉末照片图右下角为硒质量百分含量柱状图，通过原子荧光光谱仪检测得到。一方面证明本发明人实现了硒掺杂含量可控这一技术。另一方面证明本发明方案复合材料的硒含量比现有的金属有机框架都高，当质量比ZIF-67:硒粉＝1:1时，硒质量百分含量达46.7％。
图2是ZIF-8粉末与本发明不同硒含量掺杂的Se/ZIF-8复合体系材料的透射电镜图与粉末照片。分别取质量比ZIF-8:硒粉＝1:1，ZIF-8:硒粉＝5:1，ZIF-8:硒粉＝10:1，ZIF-8:硒粉＝20:1，ZIF-8:硒粉＝40:1，可见当粉末照片图右下角为硒质量百分含量柱状图，通过原子荧光光谱仪检测得到。一方面证明本发明人实现了硒掺杂含量可控这一技术。另一方面证明本发明方案复合材料的硒含量比现有的金属有机框架都高，当质量比ZIF-8:硒粉＝1:1时，硒质量百分含量达47.6％。
图3是本发明金属有机框架负载硒原子的纳米复合材料，对应Se:ZIF-67＝1:5时的元素分析图谱。图4是本发明金属有机框架负载硒原子的纳米复合材料，对应Se:ZIF-8＝1:5时的元素分析图谱。可见从硒元素的图谱与MOF中配体N元 素以及对应金属元素的图谱重叠结果得到硒与MOF的很好的结合了。
图5是本发明金属有机框架负载硒原子的纳米复合材料，对应不同质量比(Se:ZIF-67)的XRD图谱。图6是本发明金属有机框架负载硒原子的纳米复合材料，对应不同质量比(Se:ZIF-8)的XRD图谱。
从图5，图6的X射线衍射图谱，从中可以分析出本发明复合材料所具有的特征晶面信息，即不同材料具有不同的晶面信息。通过分析对比有或没有硒掺杂的MOF材料对应的晶面信息，发现硒掺杂后MOF的基本晶面信息均保留，并且没有显示新的晶面信息，复合材料的硒掺杂成功。
图7是使用ABTS总抗氧化能力检测法进行检测不同质量比(Se:ZIF-67)的基于金属有机框架含硒纳米复合材料的抗氧化能力，可见基于金属有机框架的含硒纳米复合材料具有显著的抗氧化能力，100ug/mL可以达到接近95％的清除效果。
另外使用ABTS总抗氧化能力检测法对***钠、硒酸钠、硒代半胱氨酸、硒代蛋氨酸、壳聚糖修饰纳米硒、香菇多糖修饰纳米硒和基于金属有机框架的含硒纳米复合材料的抗氧化能力进行检测。其中***钠、硒酸钠、硒代半胱氨酸、硒代蛋氨酸、壳聚糖修饰纳米硒、香菇多糖修饰纳米硒均显示低于5-10％的抗氧化效果。
图8是选取了人脑神经母细胞瘤细胞(SH-SY5Y)细胞系作为细胞模型的对象，通过加入20μM叔丁基过氧化氢模拟细胞产生的自由基，最后通过流式细胞仪检测SH-SY5Y细胞的细胞凋亡比例，来评价金属有机框架负载硒原子的纳米复合材料在自由基损伤模型对细胞损伤模型中对SH-SY5Y细胞的保护作用。由图8细胞照片可以看出，在叔丁基过氧化氢损伤后的细胞细胞凋亡比例约为50-70％，加入了复合体系细胞凋亡比例明显相对于损伤组和单独MOF组均下降明显，说明金属有机框架负载硒原子的纳米复合材料能够有效保护细胞，免受细胞遭受自由基的损伤。
本发明还提供上述制备方法得到一种金属有机框架负载硒原子的纳米复合 材料在生物制药方面的应用。所述金属有机框架负载硒原子的纳米复合材料可制成有治疗脑卒中作用的口服试剂药物或静脉注射药物，大大扩展了基于金属有机框架的含硒纳米复合材料的应用领域，具有广阔的医学药物应用前景。
本发明方案相对于现有技术具有如下的优点及效果：
(1)本发明制备方法得到的金属有机框架负载硒原子的纳米复合材料，比如Se/ZIF-67复合体系材料，或者是Se/ZIF-8复合体系材料，是把具有催化能力的MOF纳米材料与硒相结合，充分发挥纳米硒具有抗氧化，清除自由基和抗炎的功能，以及金属有机框架材料大比表面积、高孔隙率等优点。复合材料比表面积大，负载量大，通过高分辨透射电子显微镜下的元素分析，发现硒在MOF中均匀分布，表面硒的成功掺杂，而且MOF基本保持原本的形貌框架，比现有制备方式的MOF与硒的结合材料更优异。
(2)对比现有的两种基于MOF含硒的制备方法，本发明制备方法特别采用抽真空封管的形式让硒在高温加热时不会排出，还通过几百次试验发现，在高温真空密封加热至230-280℃，并保持恒温一段时间，ZIF-8粉末或ZIF-67粉末分别与纳米硒粉的融合反应效果最佳，而且是在密闭空间内随着温度的降低实现硒与MOF材料95％以上的紧密结合，没有泄露，复合材料的硒掺杂含量达35-48％。
发明人试验发现高温真空密封加热至230-280℃可防止材料和空气中氧气反应，提高材料纯度和催化率，而且如果温度低于230℃，MOF和硒不能很好结合；如果温度高于280℃，复合材料的孔隙率变小，催化率低。
(3)发明人制备的金属有机框架负载硒原子的纳米复合材料具有高的硒原子利用度，达到80-95％，对比于在管式炉中烧制的硒MOF材料，硒利用率提高20-70％，可有效减少原料浪费实现高效转化利用，为大规模合成硒MOF纳米材料提供一种创新的方案。
(4)发明人制备的金属有机框架负载硒原子的纳米复合材料相对于经过700℃以上制备的硒MOF复合材料具有更佳的水溶性、水分散性，以及更佳的 抗氧化效果，在同样硒含量条件下，抗氧化活性提高30-70％。
(5)发明人制备的金属有机框架负载硒原子的纳米复合材料相较于单独的纳米硒、MOF或经过700℃以上制备的硒MOF复合材料具有更佳的人神经母细胞瘤细胞保护效果，在脑卒中治疗中具有良好的治疗效果。

Claims (10)

  1. 一种高效制备金属有机框架负载硒原子的纳米复合材料方法，其特征在于，包括步骤：
    称取ZIF-67粉末和纳米硒粉，其质量比ZIF-67粉末:硒粉＝1-50:1，混合均匀后倒入加热容器中，将所述加热容器抽成真空状态，高温密封加热至230-280℃，并保持恒温一段时间，自动冷却后取出所述加热容器，倒出混合物得到金属有机框架负载硒原子的纳米复合材料；
    或者，称取ZIF-8粉末和纳米硒粉，其质量比ZIF-8粉末:硒粉＝1-50:1，混合均匀后倒入加热容器中，将所述加热容器抽成真空状态，高温密封加热至230-280℃，并保持恒温一段时间，自动冷却后取出所述加热容器，倒出混合物得到金属有机框架负载硒原子的纳米复合材料。
  2. 根据权利要求1所述一种高效制备金属有机框架负载硒原子的纳米复合材料方法，其特征在于，所述加热容器是石英玻璃管，抽成真空的石英玻璃管通过氢火焰高温密封，将密封好的石英玻璃管置于高温炉内，升温至230-280℃，并保持恒温一段时间。
  3. 根据权利要求1所述一种高效制备金属有机框架负载硒原子的纳米复合材料方法，其特征在于，利用真空封管***将石英玻璃管抽至真空，利用氢火焰加热石英玻璃管3-5分钟，内玻璃塞与玻璃壁贴合，直至密封完好。
  4. 根据权利要求1所述一种高效制备金属有机框架负载硒原子的纳米复合材料方法，其特征在于，还包括制备ZIF-67粉末，或者ZIF-8粉末的步骤，
    其中制备ZIF-67粉末，取六水合硝酸钴倒入烧杯A中，加入甲醇混合；另外将2-甲基咪唑倒入烧杯B中，加入甲醇混合；上述烧杯A和烧杯B中溶液分别在超声波处理下充分溶解；再将烧杯A和烧杯B中溶液倒入大烧杯混合在 一起，密封烧杯口后在剧烈搅拌下反应6-10小时，离心旋转处理，收集产物并用甲醇清洗，干燥后得到ZIF-67粉末；
    制备ZIF-8粉末，取六水合硝酸锌倒入烧杯A中，加入甲醇混合；另外将2-甲基咪唑倒入烧杯B中，加入甲醇混合；上述烧杯A和烧杯B中溶液分别在超声波处理下充分溶解；再将烧杯A和烧杯B中溶液倒入大烧杯混合在一起，密封烧杯口后在剧烈搅拌下反应1-2小时，离心旋转处理，收集产物并用甲醇清洗，干燥后得到ZIF-8粉末。
  5. 根据权利要求1所述一种高效制备金属有机框架负载硒原子的纳米复合材料方法，其特征在于，根据控制所述ZIF-67粉末和纳米硒粉混合比例，或者根据控制ZIF-8粉末和纳米硒粉混合比例，可调节所述金属有机框架负载硒原子的纳米复合材料的硒掺杂含量达35-48％。
  6. 一种金属有机框架负载硒原子的纳米复合材料，其特征在于，是采用权利要求1-5中任意一项制备方法得到。
  7. 根据权利要求6所述一种金属有机框架负载硒原子的纳米复合材料，其特征在于，是Se/ZIF-67复合体系材料，或者是Se/ZIF-8复合体系材料。
  8. 根据权利要求6所述一种金属有机框架负载硒原子的纳米复合材料，其特征在于，所述金属有机框架负载硒原子的纳米复合材料具有抗氧化作用。
  9. 采用权利要求1-5中任意一项制备方法得到一种金属有机框架负载硒原子的纳米复合材料在大脑疾病、生物制药方面的应用。
  10. 根据权利要求9所述应用，其特征在于，所述金属有机框架负载硒原子的纳米复合材料，具有人神经母细胞瘤细胞保护作用，可制成有治疗脑卒中 作用的口服试剂药物或静脉注射药物；或者所述金属有机框架负载硒原子的纳米复合材料可用于生物催化治疗应用中。
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